Noncorrosive lubricating composition



4 improved metal-working lubricants.

' ing trades.

Patented Dec. 2,1947

UNITED .FSTATES. PATENT." OFFICE NONCORROSIVE COMPOSITION Gifford D. Davis,South Orange, N. J., and Edwin J. Barth, Cody,'Wyo:, asslgnors to Nopco Chemon, N. J., a corporation of ical Company, Harris New Jersey- LUBRICATING 3 Claims. (01. 252-485) The present invention relates to mineral oils containing sulfurized glyceryl esters of tall oils. It is'wellknown that various oils, when treated with sulfurizing agents, acquire very desirable lubricating properties, and a wide variety of such duction of novel sulfurized compositions havin improved properties and low cost.

An object of the invention is to provide improved lubricants.

A second object of the invention is to provide A third object of the invention is to provide improved extreme pressure lubricants.

It has been discovered by this invention that the glyceryl esters of tall oil may be treated with .sulfurizing agents to yield products which are characterized by very desirable lubricating properties, notably oilin'esstehacity, wetting ability vention may be made by the use of any customary sulfurizing agent, the sulfurizing reaction proceeding smoothly and without untoward side re-' actions.- Moreover, the starting material, the glycerylesters of tall oil, may be made from the readily and cheaply procurable tall oil. By reason of these factors, this invention provides satisfactory and cheap sulfurized products which have come into extensive use in the metal work- The tall oil glyceride starting materials of this invention may be produced by esterifying, with glycerine, any of the various grades of crude, re-

I 2 glyceryl esters afford a cheap and readily available starting material for use in this invention.

As stated above, any of the usual sulfurizing reagents and procedures are effective in the treatment of tall oil to produce sulfurized compositions according to this invention, treatment with sulfuryl halides, sulfur oxyhalides, active sulfur or elementary sulfur being suitable, the lastnamedtreatment being preferred on account of its simplicity, cheapness and independence of special techniques or apparatus. In general, treatagitating and heating the esterifled tall oil together with between about 2 and about 20% of sulfur, based on the total charge, at temperatures between about 300 and about 380 F. preferably in the neighborhood of 350 F. for from about 4 to about 10 hours. If only a small amount of sulfur-say from 2% to 5%is to be incorporated, practically the entire quantity of sulfur may be incorporated at the very beginning or the reaction; on. the other hand, when greater proportions of sulfur-say from 7% to 10 %--are incorporated, it is preferred to induce the reaction by adding the sulfur in small portions over a period of two "hours orso. With greater proportions of'sulfur, the addition of sulfur will be carried out over correspondingly longer periods of time; precaution should be taken, however. to avoid undue prolongation of the period of sulfur addition, since undesirable side reactions are apt to occur when this is done.

Following the sulfurization reaction, the mass is preferably blown with air or an inert gas, so as to remove any disagreeable-smelling volatile material which may have been developed therein.

fined and/or distilled tall oils, which are well a known products abundantly produced incidentally to the various alkaline wood pulping processes. The esteriflcation of these materials with glycerine to furnish the glyceride starting materials employed in this invention may be eflected in accordance with known esteriilcation procedures, one very satisfactory process for this purpose being disclosed in the patent to Segessemann No. 2,278,674, involving a simple heating together of glycerol and tall oil, with or without the presence of a catalyst such as ZnO. On account of the cheapness and abundance of tall 011, and in view of the simplicity of the esteriflcation processes applicable thereto, it is evident that the tall 011 The resultant sulfurized products are characterized by highly desirable lubricating properties, including oiliness, wetting power, tenacity and extreme pressure properties. The sulfurized products are extensively soluble in a wide variety of paraflinic, and especially naphthenic, lubricat ing oils, and when so dissolved impart desirable lubricating qualities to, the'compositions as a whole. Such blends are particularly useful as metal-working oils such as cutting, boring, drilling, sewing, and die lubricants. The products are erty of forming tenacious films upon the surface of metallic objects, so as to prevent the corrosion thereof during processing and/or storage.

ment'with elementary sulfur is carried out by 3 Following are exemplary procedures for the manufacture of sulfurized compositions according to this invention, all parts given being by weight.

Example I Parts Glyceryl esters of tall 011 83 Sulfur 17 The tall oil esters were heated to 330 F. in a steam jacketed kettle provided with a stirring mechanism, the temperature being maintained, and the stirring being continued, for 4 hours. The sulfur was added gradually during this period-according to the schedule:

Parts During the first hour 8 During the next 1 hours During the next /2 hour 2 During the next hour: 2

At the end of this 4-hour induction period, the temperature was raised to 350 F., and this temperature maintained and stirring continued for 2 hours to finish the reaction. Thereafter the batch was cooled to 200 F., and air was blown through the charge for two hours to remove any malodorous and unstable lay-products of the reaction. Finally, the charge was drained from the vessel and cooled. The product so produced was found to contain the sulfur in firmly-combined form, showing no tendency to decompose over long periods of time even at somewhat elevated temperatures.

20 parts of the sulfurized tall oil produced as just described were blended with 80 parts of a naphthenic lubricating oil. The resultant blend was found highly suitable as a lubricant in cutting, milling, sawing, broaching, drawing and like metal-working processes. The blend had, moreover, the property of forming a tenacious film over metallic surfaces treated therewith, so as to prevent corrosion thereof during subsequent proc essing and storage. The blend was absolutely noncorrosive to metallic surfaces at ordinary temperatures and made no attack upon copper, steel, or brass surfaces at temperatures as high as 400 F., other than to form a thin, smooth black sulfide film thereon.

Example II Parts Glyceryl esters of tall oil 91 Sulfur V 9 The tall oil esters and sulfur were mixed cold in a jacketed kettle provided with an agitator. With continued agitation, the temperature of the mass was gradually raised to 250 F. over a period of 1 /2 hours. Thereafter, with further continued stirring, the temperature was raised to 320 R, which temperature was maintained for 2 hours, at the end of which time the sulfur was complete ly reacted. The charge was cooled to 200 F, and blown with air for 1 hour. The charge was then drained out and cooled. A blend of 20 parts of properties and stability characteristics of the blend made in accordance with Example I.

Example III Parts Glyceryl esters of tall oil Sulfur 5 Example IV Parts Glyceryl esters of tall oil 87 Sulfur 13 The above ingredients were mixed cold in a jacketed kettle provided with an agitator. With continued agitation, the charge was heated according to the program:

. "15 First hour 200 Next 1 /2 hours 300 Next 2 /2 hours 320 The charge was then cooled to 200 F., blown with air for 2 hours, drained oil, and cooled. The product had substantiall the same uses and properties as the product of Example I.

From the foregoing general discussion and specific examples, it will be seen that there are provided by this invention novel sulfurized compositions, having technically desirable lubricating and anticorrosion properties. The products may, moreover, be made from the readily procurable tall oil glycerides and sulfur, by the use of ordinary equipment and techniques.

The present application is a division of Serial No. 489,466, filed June 30, 1943, now Patent No. 2,385,912, dated October 2, 1945.

What is specifically claimed and desired to be secured by Letters Patent is:

1. A noncorrosive lubricating composition, the essential constituents of which consist of a mineral lubricating oil and sulfurized glyceryl esters of tall oil, the mineral oil constituting the major portion of the composition and said sulfurized glyceryl esters of tall oil being present in an amount sufficient to impart extreme pressure properties to the composition.

2. The lubricating composition of claim 1 wherein the mineral lubricating oil is naphthenic.

3. The lubricating composition of claim 1 wherein the mineral lubricating oil is parafiinic.

- GIFFORD D. DAVIS.

EDWIN J. EARTH.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,172,285 Lincoln 1. Sept, 5, 1939 2,198,562 Pollak Apr. 23, 1940 2,204,538 Lincoln June. 11, 1940 

